Dyeing with azo dyes



Patented May 6, 1930 UNITED STATES PATENT,

OFFICE JAMES BADDILEY, PERCY CHORLEY, AND RAINALD BRIGHTMAN, OF MANCHESTER,

ENGLAND, ASSIGNORS TO BRITISH DYESTUFFS CORPORATION LIMITED, OF MAN- CHESTER, ENGLAND, COMPANY OF GREAT BRITAIN AND IRELAND DYEING WITH AZO DYES No Drawing. Application .flled March 16, 1927, Serial No. 175,925, and in Great Britain April 16, 1926'.

By this invention regenerated cellulose silks, such as viscose silk, are dyed 1n level shades with the dyestuffs obtained by combining suitable diazo compounds with compounds of the type no on no, i 50.1;

is obtained when oxalyl chloride is gradually added to a well-stirred solution of the sodium salt of EZ-amino-8-naphthol-6-sulphonic acid in presence of excess of sodium acetate. The product is isolated'by addition of common salt. Similarly, 8: 8-dihydroxy-2 2'-dinaphthyl alpha gamma diamino acetone-6 6'-disulphonic acid.

Nrronacoonarrn tom son is obtained when a neutral solution of 478 parts of 2-amino-8-naphthol-6-sulphonic acid is added to a solution of 250 parts of alphagamma-dichloracetone in alcohol and the mixture heated at about 50 C. in presence of excess sodium acetate for several hours. The alcohol is. then'distilled off and the product isolated by addition of common-salt.

As suitable diazo components there may be used aniline and its homologues or substitution products, including the sulphonic and carboxylic acids, and also naphthylamines and their sulphonic acids. For example, there may be used aniline, ortho anisidine, meta aminobenzoic acid, sulphanilic acid, p-aminoacetanilide, p-chloraniline, p-nitroaniline and naphthionic acid, but it must be understood that our invention is not limited to these'examples. The dyestuffs may be made by combining one or two molecules of a diazo com- Some ofthe dyestuffs of the aforementioned types are already known but they have not been adopted in the dyeing industries, probably because they possess only a poor affinity for cotton and have therefore no value for dyeing the cotton fibre. It was not to be foreseen that these dyestuffs would have a good aflinity for regenerated cellulosesilk, such as viscose silk, and in particular that they would have the property of dyeing such silks in level shades.

. It is well known that the artificial silks made from regenerated cellulosegive great difficulty in dyeing, owing to the fact that the fabric generally possesses an uneven avidity for the usual types of substantive cotton colours in consequence of which the 1 dyeings obtained are unlevel. Our invention Emample 1.The dyebath is made up from 4 3000 parts of water, 15 parts of Glaubers salt, 3 parts of soap and 2 parts of the symmetrical dyestuif obtained in the known manner by combining two molecules of otoluidine with one'molecule of 8:8 -dihy- The components described have the propdroxy-2:2-dinaphthylurea-6:6'-disulphonic erty of coupling once in weak acid media acid and which, in the form of its sodium salt, may be represented by the formula (such as acetic acid) or twice in alkaline media. For unsymmetrical couplings we used in this example there be used the dyestufl obtained by combining one molecule of para-anisidine' and one molecule of naphthionic acid with 1 molecule of 8:8'-dihydroxy -2 2 dinaphthyl-alpha-beta-ethylenediamine-6: 6-disulphonic acid the silk is dyed an even red-brown shade. The dyeings obtained possess good fastness properties.

Other examples illustrating our invention are quoted in the following table therefore use a'weak acid for the first coupling and an alkali for the second.

What we claim and desire to secure by Letters Patent is 1. The process of dyeing regenerated cellulose materials in even, level shades which comprises applying to the said regenerated cellulose materials the azo dyes obtained by coupling X molecular proportions of a diazo compound with one-molecular proportion of a compound having the general structural formula wherein R represents a CO or -CS- group, or a straight chain composed of two methylene or carbonyl groups or a combination of a carbonyl group with one or two methylenev groups, and X is 1 or 2.

being hydrolyzed eiter coupling, in order to remove the acetyl groups Aniline (2 molecules) dlsulphonlc acid m-eminobenzoic acid (2 molecules) Do. p-aminoaceteniiide (2 molecules) the colour Do.

being hydrolyzed alter coupling in order to 8:8 dihydroxy 3 2:2 dinaphthylthiourea 6:6-

Compound diazotized Coupling component Shade on viscose silk Aniline (2 molecules) 8:8 dihydroxy 2:2 dinaphthylurea 6:6 di- Yellowish-red sul honic acid m-xylidine (2 molecules) 0. Red m-xylidine (1 molecule) D0. Red, changed to reddish-brown when deyleloped with diazotized p-nitroam me -nltroaniline (1 molecule) D0, Reddish-brown, becoming yellower when developed with diazotized p-nitroeniline o-enisldine (2 molecules) Do. Crimson Arzilinelflufiolecule) and p-eminoaceteniilde Do. Scarlet lmoec e A1(1ilinel(1 uzpglemlle) and m-amlnobenzoic acid D'o. Scarlet mo ec e Aniline (1 molecule) 8:8 dihydro 2:2 dlnaphthyluree 6:6 di- Scarlet I sulphonice d Anilipe 1)molecule) and naphthionie acid (1 Do. Red

mo ec e Angliiae (1 molecule) and m-xylidine (1 mole- Do. Red

c e p-chloroeniline 2 molecules) Do. Red p-aminoacete de (2 molecules),the.colour Do. Violet. Dizaotized on the fibre and developed with fl-naphthol, gives a blue-black shade. Developed with m-toluylenediamine gives a black shade, and with fl-oxynaphthoic Ragid, a brown shade Red Violet. Diazotized on the fibre and developed with B-naphthol gives a remove the acetyl groups blue-black shade. Developed with nlil-tgluylenediemine, gives a black s a e hioroeniline (2 molecules) 8:8 dihydroxy -.2:2' dinephthyl a B- ethyl- Brown M enediamine-G:G-disulphonic acid o-anisidine (2 molecules). Do. Brown p-emlnoecet de (2 molecules), the acetyl Do. Violet-brown groups being hydrolysed after coupling p-chloroeniiine (2 molecules) NzN 8:8 dihydroxy 2:2 dinaphthylglyci- Red nemide-6:6-d1sulphonlc acid Sulplnmflic acid (2 molecules) NzN 8:8 dihydroxy 2:2 dinaphthylglyci- Red nemide-flzfi' disulphonic acid p-elfloroenlline (2 molecules) 8% dihydrdxy 7 2:2 dinaphthyloxemide 6:6- Pink dlsulphdnic acid p-chloroeniline (2 molecules) N:N 8:8 dihydroxy 2:2 -edinephthyl.- a Reddisbbrown gemma-diemino-ecetone-mo disulphonic acid 4-chloro-2-enieidine (2 molecules) Do. v Brown.

2. The process of dyeing regenerated cellulose materials in even, level shades which comprises applying to the said regenerated cellulose materials the azo dyes obtained by coupling two molecular proportions of a diazo compound with one molecular proportion of a compound having the general formula where R represents a CO- or -CS group, or a straight chain composed of two methylene or carbonyl groups or a combination of a carbonyl group with one or tw methylene groups.

3. The process of dyeing regenerated cellulose materials in even, level shades which comprises applying to the said regenerated cellulose materials the azo dyes obtained by coupling two molecular proportions of a diazo compound with one molecular proportion of a compound having the general formula HO OH H H l wherein, R. represents CO, CS-, CHZCHZ' OI "GH2 COCH groups.

4. The process of dyeing regenerated cellulose materials. in even, level shades which comprises applying to the said regenerated cellulose materials the azo dyes obtained by coupling two molecular proportions of a diazo compound with one molecular proportion of a compound having the general formula OH -H H H035 SOsH' wherein R represents CO- or -CS- groups.

5. The process of dyeing regenerated cel-v lulose materials in even, level shades which comprises applying to the said regenerated cellulose materials the azo dyes obtained by coupling two molecular proportions of a diazo compound with one molecular proportion of8 8-dihydroxy-2 2'-dinaphthylurea--6 6- sulphonic acid.

6. The regenerated cellulose materials dyed with the azo dyes obtained by coupling X molecular proportions of a diazo compound with one molecular proportion of a compound having the general structural formula HOaS 80 B.

HO OH i --RN H0 8 SOaH wherein R represents a -CO- or --CS- group, or a straight chain composed of two methylene or carbonyl groups or a combination of a carbonyl group with one or two methylene groups.

8. The regenerated cellulose materials dyed withthe azo dyes obtained by coupling 2 mols of a diazo compound with one mol of a compound having the general structural formula HO OH r N-R-N HO: SO H wherein R represents -CO-, -CS,- OH2CH2, 01' 'CHg COCH groups.

9. The regenerated cellulose materials dyed with the azo dyes obtained by coupling two molecular proportions of a diazo compound with one molecular proportion of a compound having the general formula HO OH N-R-N SOaH wherein R represents -CO-- or -CS-- groups.

10. The regenerated cellulose materials dyed with the azo dyes obtained by coupling two molecular proportions of a diazo compound with one molecular proportion of 8 8- dihydroxy- 2 2' dinaphthylurea 6 6' disulphonic acid.

In testimony whereof we affix our signatures.

JAMES. BADDILEY. PERCY CHORLEY. RAINALD BRIGHTMAN. 

